Heteroatom containing 3,3-bis-perfluoroalkyl oxetanes and polyethers therefrom

ABSTRACT

Heteroatom containing perfluoroalkyl terminated oxetanes of the formula &lt;CHEM&gt; are prepared from 3,3-dihalogenated oxetanes and thiols of the formula Rf-E-SH, amines of the formula Rf-E-NH-R, alcohols of the formula Rf-E-OH or perfluoro-amides, wherein Rf is a straight chain perfluoroalkyl of 1 to 18 carbon atoms. The reaction products of these fluorinated oxetanes with nucleophiles are disclosed, as are certain functional derivatives. These products may serve as intermediates or have utility in their own right. Fluorinated polyethers derived therefrom are disclosed and include random or block compositions containing the residue from at least one Rf oxetane, containing two perfluoroalkyl hetero groups.e (ücontaining two perfluoroalkyl hetero groups. These polyethers provide improved thermal stability and useful low surface energy oil and water repellent coatings for textiles, glass, paper, leather and other materials.

BACKGROUND OF THE INVENTION

This invention relates to hetero group containing perfluoroalkylterminated oxetanes, their reaction products with nucleophiles, relatedhalogenated derivatives, and derived polyethers. Their primary use is toimpart oil and water repellency to textiles, glass, paper, leather, andother compositions.

Oxetanes connected by sulfur atoms to bis-perfluoroalkyl substituentshave not been reported. Oxetanes connected by oxygen atoms to branchedperfluoroalkyl groups or to fluoroalkyl groups with terminal hydrogenatoms have been described by C. Krespan in J. Org. Chem. 43, 4 (1978),Ger. Offen. 2,109,966 and 2,116,105, and by Vakhlamova, L. in C. A.89:110440p and 85:62609.u.:

However, fluoroalkyl compounds which are terminally branched or containomega-hydrogen atoms do not exhibit efficient oil repellency.Perfluoroalkyl compounds which are connected directly via hetero-atomswithout alkylene spacers are not sufficiently flexible as pendantgroups. Perfluoroalkylmethylene-hetero groups, other thantrifluoroethylene, are expensive to prepare. Consequently, suchfluoroalkyl oxetanes are not practical intermediates from which toobtain useful products. Additionally, other perfluoroalkyl compoundscontaining heteroaromatic connecting groups or mono-fluoroalkyl oxetanescontaining oxygen have been reported e.g. J. Org. Chem. 45 (19) 3930(1980). These compounds are not useful for purposes of this invention.

The subject perfluoroalkyl oxetanes are readily isolated in high yieldand purity. Since the subject oxetanes are connected to the linear,pendant perfluoroalkyl chains by flexible hetero groups, more mobileperfluoroalkyl functions are provided, which exhibit optimal oilrepellency.

Bis-perfluoroalkyl oxetanes, polymeric derivatives thereof, and theirreaction products with nucleophiles are useful because they possess alow free surface energy which provides oil and water repellency to awide variety of substrates. Oxetanes containing a single R_(f)-function, multiple R_(f) -functions with terminal hydrogen atoms, orbranched perfluoroalkyl groups are known, but do not provide theseproperties to the same extent. The subject oxetanes may be prepared inhigh yield and purity in contrast to prior art materials.

DETAILED DISCLOSURE

This invention relates to a method of making 3,3-bis-perfluoroalkylsubstituted R_(f) -oxetanes and their derived polyethers. In oneembodiment, the polymers are homopolymers. In another they are blockpolymers and contain 1%-90% of a fluorochemical block connected to99%-10% by weight of a non-fluorochemical block. This invention alsorelates to the reaction products of said oxetanes with nucleophiles toform neopentyl alcohols. Other aspects of this invention are thesubstitution of the alcohol function by halide and the derivatization ofthe alcohols as esters or urethanes. The compositions are useful per seor intermediates for coatings on textiles, glass, linoleum, leather,wood, tile, metals, plastics and other various materials.

This invention most generally relates to novel heteroatom containingperfluoroalkyl terminated neopentyl oxetanes and derived polymerscontaining residues from said R_(f) -oxetanes.

Another aspect of this invention relates to a substrate containing 0.01%to 10% by weight of a fluorine-containing polyether composition, atleast part of said fluorine being provided by one or more units derivedfrom the heteroatom containing R_(f) -neopentyl oxetane, to become oiland water repellent.

The novel heteroatom containing R_(f) -neopentyl oxetanes have thegeneral formula I or II ##STR3## wherein R_(f) is a straight chainperfluoroalkyl of 1 to 18 carbon atoms, E is branched or straight chainalkylene of 2 to 10 carbon atoms, or said alkylene interrupted by one tothree groups selected from the group consisting of --NR--, --O--, --S--,SO ₂ --, --COO--, --OOC--, --CONR--,--NRCO--, --SO₂ NR--, and --NRSO₂--, or terminated at the R_(f) end with --CONR-- or --SO₂ NR--, whereR_(f) is attached to the carbon or sulfur atom, or R_(f) -E istrifluoroethylene, i.e. CF₃ CH₂ and for formula I, X is --S--, --O--,--SO₂ --, or --NR--, or for formula II, X is --CONR--, --SO₂ NR--, or adirect bond where R_(f) is attached to the carbon or sulfur atom, andwhere R is independently hydrogen, alkyl of 1 to 6 carbon atoms orhydroxyalkyl of 2 to 6 carbon atoms.

Further, the 3,3-substituents need not be identical, though identicalgroups are preferred.

Novel polymers are derived from the aforementioned oxetanes.

It is understood that the R_(f) group usually represents a mixture oflinear perfluoroalkyl moieties. When the R_(f) group is identified ashaving a certain number of carbon atoms, the said R_(f) group alsousually concomitantly contains a small fraction of perfluoroalkyl groupswith a lower number of carbon atoms and a small fraction ofperfluoroalkyl groups with a higher number of carbon atoms.

Preferably the instant compounds of formula I are those where R_(f) isperfluoroalkyl of 2 to 12 carbon atoms , E is alkylene of 2 to 6 carbonatoms, --CONHCH₂ CH₂ --, --CH₂ CH₂ N(CH₃)CH₂ CH₂ --, --CH₂ CH₂ SO₂ NHCH₂CH₂ --, --CH₂ CH₂ OCH₂ CH₂ --, or --SO₂ NHCH₂ CH₂ --, and X is--S--,--SO₂ -- or --O--. A preferred embodiment is where R_(f) is amixture of C₄ F₉, C₆ F₁₃, C₈ F₁₇ and C₁₀ F₂₁.

Most preferred are those compounds of formula I where R_(f) isperfluoroalkyl of 6 to 12 carbon atoms, E is ethylene, and X is S, i.e.,##STR4##

In another group of most preferred compounds R_(f) is perfluoroalkyl of6 to 12 carbon atoms, E is ethylene, and X is 0, i.e., ##STR5##

The novel R_(f) -oxetanes can be obtained directly by the reaction of aperfluoroalkyl thiol of formula R_(f) -E-SH, perfluoroalkyl amine offormula R_(f) -E-NR₂, perfluoroalkanol of formula R_(f) -E-OH, or aperfluoroalkylsulfonamide of formula R_(f) -SO₂ NHR with a bis-haloalkyloxetane of formula ##STR6## where Y is Cl, Br, or I.

In one preferred embodiment, the starting material is bis-bromomethyloxetane and has the formula ##STR7##

This intermediate is commercially available in high purity. Dichloro anddiiodo neopentyl oxetanes have also been reported.

The synthesis of R_(f) -oxetanes proceeds by the nucleophilicsubstitution of a perfluoroalkyl substituted thiol, alcohol, sulfonamideamine for halide. The reaction is preferably conducted in an aqueoussystem using phase transfer catalysis for the thiolate and amine. Analternate process, in anhydrous media, is best for the alcohol andinvolves the combination of:

a. an aprotic solvent, such as N-methylpyrrolidone,N,N-dimethylformamide, dimethyl sulfoxide, or the like, or ketones, suchas acetone, methyl alkyl ketones, or dialkyl ketones.

b. moderate reaction temperature, on the order of 50° C. to about 120°C., and

c. a stoichiometric quantity of an anhydrous alkaline earth carbonate,preferably potassium carbonate, in the ratio of 1 mole of carbonate permole of halide to be displaced.

With certain amines, tertiary amine catalysis is useful, as exemplifiedby triethylamine, tributylamine, dimethylaminopyridine, or piperidine.With alcohols or sulfonamides, Crown ether catalysis is useful asexemplified by 12-Crown-4, 15-Crown-5, and 18-Crown-6.

The reaction temperature and choice of solvent are mutually dependent. Areaction temperature in the range of 50° C.-140° C. is one wherein theformation of undesirable by-products is minimized and the reactionproducts are stable. Conditions are adjusted in order to achieve areasonable rate of reaction at the chosen temperature.

In the synthesis of the R_(f) -oxetanes, by-products may be present.When the starting thiol is R_(f) CH₂ CH₂ SH and bis-bromomethyl oxetaneis used, the by-products include ##STR8##

Such an intermediate is consistent with the general reaction conditions.It should be noted that the ready oxidation of thiols to disulfidesrequires that the chemistry be conducted in an inert atmosphere.

The subject oxetanes can also be made by first reacting thebromo-oxetane intermediates with a functional thiol or amine, i.e. HSCH₂CH═CH₂, HSCH₂ COOH or NH₂ CH₂ CH═CH₂. The resultant sulfide or amine canthen be reacted with the R_(f) -containing moiety by a suitablechemistry which does not involve the pendant oxetane. The reactant maybe R_(f) I, R_(f) CH₂ CH₂ I, R_(f) CH₂ CH₂ OH or a like monofunctionalR_(f) -reactant. If iodine atoms are introduced they may be removed byreduction, dehydrohalogenation, or coupling.

For example, ##STR9##

The subject sulfido- oxetanes can be readily oxidized to thecorresponding bis-sulfone oxetanes by peracetic acid (H₂ O₂ /aceticacid) or by other conventional oxidants. With peracetic acid,temperatures of 30° C.-100° C. are appropriate depending on the amountof excess oxidizing agent to ensure that the intermediate sulfoxides arecompletely oxidized.

Perfluoroalkyl thiols useful herein are well documented in the priorart. For example, thiols of the formula R_(f) -E-SH have been describedin a number of U.S. Pat. Nos. including 3,655,732 and 4,584,143.

Thus, U.S. Pat. No. 3,655,732 discloses mercaptans of formula R_(f)-E-SH where

E is alkylene of 1 to 16 carbon atoms and R_(f) is perfluoroalkyl, andteaches that halides of formula R_(f) -E-Halide are well-known; reactionof R_(f) I with ethylene under free-radical conditions gives R_(f) (CH₂CH₂)_(a) I while reaction of R_(f) CH₂ I with ethylene gives R_(f) CH₂(CH₂ CH₂)_(a) I as is further taught in U.S. Pat. Nos. 3,088,849;3,145,222; 2,965,659 and 2,972,638.

U.S. Pat. No. 3,655,732 further discloses compounds of formula R_(f)-R'-Y-R"-SH where

R' and R" are alkylene of 1 to 16 carbon atoms, with the sum of thecarbon atoms of R' and R" being no greater than 25; R_(f) isperfluoroalkyl of 4 through 14 carbon atoms and Y is --S-- or --NR'''--where R''' is hydrogen or alkyl of 1 through 4 carbon atoms.

U.S. Pat. No. 3,544,663 teaches that the mercaptan R_(f) CH₂ CH₂ SHwhere R_(f) is perfluoroalkyl of 5 to 13 carbon atoms, can be preparedby reacting the perfluoroalkyl alkylene iodide with thiourea or byadding H₂ S to a perfluoroalkyl substituted ethylene (R_(f) --CH═CH₂),which in turn can be prepared by dehydrohalogenation of the R_(f) --CH₂CH₂ -- halide.

The reaction of the iodide R_(f) -E-I with thiourea followed byhydrolysis to obtain the mercaptan R_(f) -E-SH is the preferredsynthetic route. The reaction is applicable to both linear and branchedchain iodides.

Particularly preferred herein are the thiols of formula

R_(f) CH₂ CH₂ SH where

R_(f) is perfluoroalkyl of 6 to 12 carbon atoms. These R_(f) -thiols canbe prepared from R_(f) CH₂ CH₂ I and thiourea in very high yield.

Perfluoroalkylamines useful herein are well documented in the prior art.For example, C₆ F₁₃ CH₂ CH₂ NH₂ has been described in Japan Kokai77/118,406. R_(f) CH₂ NH₂ wherein R_(f) is CF₃ through CF₃ (CF₂)₁₁ aredescribed in British Patent No. 717,232 (1954).

Further and R_(f) SO₂ NR(CH₂)_(m) NR(CH₂)₃ NH₂ and R_(f) CH₂ CH₂ SO₂NH(CH₂)_(m) NR₂ are described in G.B. 1,106,641 and U.S. Pat. No.3,838,165 respectively., R_(f) CONH(CH₂)_(m) NH₂ in Jap. Kokai 52/14767.

Perfluoroalkanols useful herein are well documented in the prior art,and many are commercially available. They have the general formula R_(f)-E-OH and include the following:

C₈ F₁₇ SO₂ N(C₂ H₅)C₂ H₄ OH

C₈ F₁₇ C₂ H₄ OH

C₈ F₁₅ CON(C₂ H₅)C₂ H₄ OH

C₈ F₁₇ C₂ H₄ SC₂ H₄ OH

C₈ F₁₇ C₂ H₄ SO₂ N(CH₃)C₄ H₈ OH

C₈ F₁₇ C₂ CH₂ SO₂ NHCH₂ CH₂ OH.

Perfluoroalkylsulfonamides useful herein are well documented in theprior art such as in U.S. Pat. No. 2,915,554 and include compounds ofthe general structure R_(f) -SO₂ NHR, such as

C₈ F₁₇ SO₂ N(C₂ H₅)OH

C₈ F₁₇ SO₂ N(C₃)H

C₈ F₁₇ SO₂ N(i-CH₃ H₇)OH

C₁₀ F₂₁ SO₂ N(C₂ H₅)H

C₁₀ F₂₁ SO₂ NH₂

The oxetanes can be used directly or indirectly by reaction withnucleophiles to make a variety of products. Such nucleophiles as halideions, thiourea, alcohols and thiols can be used as described inHeterocyclic Compounds by Weissberger, Vol 19 (II), under Oxetanes by S.Searles, Jr.

The instant invention also related to novel heteroatom containing R_(f)-neopentyl compounds having the formula III or IV ##STR10## whereinR_(f) is a straight chain perfluoroalkyl of 1 to 18 carbon atoms. E isbranched or straight chain alkylene of 2 to 10 carbon atoms, or saidalkylene interrupted by one to three groups selected from the groupconsisting of --NR--, --O--, --S--, SO₂ --, --COO--, --OOC--,--CONR--,--NRCO--, --SO₂ NR--, and --NRSO₂ --, or terminated at theR_(f) end with --CONR-- or --SO₂ NR--, where R_(f) is attached to thecarbon or sulfur atom, R_(f) -E is trifluoroethylene, and for formulaIII, X is --S--, --O--, --SO₂ --, or --NR--, or for formula IV, X is--CONR--, --SO₂ NR--, or a direct bond where R_(f) is attached to thecarbon or sulfur atom, and where R is independently hydrogen, alkyl of 1to 6 carbon atoms or hydroxyalkyl of 2 to 6 carbon atoms, and

T₁ and T₂ are independently chloro, bromo, or iodo, or where one of T₁and T₂ is hydroxyl, alkanoyloxy of 2 to 18 carbon atoms, alkenoyloxy of2 to 18 carbon atoms or benzoyloxy, and the other of T₁ and T₂ isdefined above.

When one of T₁ and T₂ is alkanoyloxy, said group is for example acetoxy,propionyloxy, butyryloxy, caproyloxy, capryloyloxy, nonanoyloxy,lauroyloxy or octadecanoyloxy.

When one of T₁ and T₂ is alkenoyloxy, said group is for exampleacryloyloxy, methacryloyloxy or oleoyloxy.

Preferably one of T₁ and T₂ is hydroxyl and the other of T₁ and T₂ ischloro, bromo, or iodo.

In another preferred embodiment, both of T₁ and T₂ are chloro, bromo oriodo, most preferably bromo.

It is understood that the R_(f) group usually represents a mixture oflinear perfluoroalkyl moieties. When the R_(f) group is identified ashaving a certain number of carbon atoms, the said R_(f) group alsousually concomitantly contains a small fraction of perfluoroalkyl groupswith a lower number of carbon atoms and a small fraction ofperfluoroalkyl groups with a higher number of carbon atoms.

Preferably the instant compounds of formula III are those where R_(f) isperfluoroalkyl of 2 to 12 carbon atoms , E is alkylene of 2 to 6 carbonatoms, --CONHCH₂ CH₂ --, --CH₂ CH₂ N(CH₃)CH₂ CH₂ --, --CH₂ CH₂ SO₂ NHCH₂CH₂ --, --CH₂ CH₂ OCH₂ CH₂ --, or --SO₂ NHCH₂ CH₂ --, and X is --S--,--SO₂ -- or --O--. A preferred embodiment is where R_(f) is a mixture ofC₄ F₉, C₆ F₁₃, C₈ F₁₇ and C₁₀ F₂₁.

Most preferred are those compounds of formula III where R_(f) isperfluoroalkyl of 6 to 12 carbon atoms, E is ethylene, and X is S.

In another group of most preferred compounds R_(f) is perfluoroalkyl of6 to 12 carbon atoms, E is ethylene, and X is 0.

Polyethers derived from non-fluorinated oxetanes are well known and arealso described by Searles in the previous citation. The derivedpolyethers are generally prepared from the corresponding oxetane monomerby cationic polymerization, most typically with a powerful electrophilesuch as boron trifluoride or its etherate. Polymerization occurs rapidlyand exothermically and is generally conducted in solution. A co-catalystof water appears necessary and high molecular weight polymers can beobtained. The polymer of 3,3-bis(chloromethyl) oxetane was knowncommercially as "Penton" and has good electrical molding, dimensionalstability and solubility properties. It is no longer manufactured.

Numerous 3,3-disubstituted oxetanes have been reported, includingseveral highly branched perfluoroalkyl derivatives, and several havebeen polymerized.

Polyethers derived from the instant linear 3,3-bis-perfluoroalkyloxetanes can also be copolymerized with tetrahydrofuran and blockcopolymers prepared by the method taught by S. V. Conjeevaram, et. al.in J. polymer Sci., 23, 429-444 (1985).

These polyethers have extremely low free surface energies and therefore,possess oil and water repellent properties, as well as mold release andother properties associated with low free surface energy. It should benoted that the compositions of this invention are characterized by thepresence of two perfluoroalkylhetero groups in close proximity, acharacteristic which provides improved oil and water repellentproperties over the fluorinated compositions of the prior art.

Furthermore the two perfluoroalkylthio groups are connected via aneopentyl moiety which does not permit the thermal elimination ofmercaptan by beta-elimination. Hence, these R_(f) -oxetanes and theirderivatives with various nucleophilic species have enhanced thermalstability. It should be noted that the reaction of oxetanes and HCl,HBr, or HI yields halohydrins.

The alcohol function of these halohydrins can be halogenated to formdihalo compounds. Other chemistries normally exhibited by alcohols canbe accomplished, such as esterification, etc.

The halohydrins or dihalo derivatives can also be reacted withmercapto-acids to yield bis-perfluoroalkyl carboxylates useful as papersizes.

Using the R_(f) -compounds and polyethers described herein, it ispossible to manufacture molds that display excellent release properties.It is also possible to prepare polymeric compositions with enhancedthermal stability.

Treatment of a textile with a fluorine-containing composition, notably abis-perfluoroalkyl containing polymer, provides outstanding oil andwater-repellent characteristics thereto.

The invention described above is illustrated by the following examples:

Examples 1 to 6 illustrate the preparation of the R_(f) -oxetanes.

Examples 7 to 11 demonstrate the wide diversity of nucleophilic reactionproducts and related compounds that can readily be prepared from thesubject oxetanes.

Example 12 demonstrates the formation of a polyether derived from anoxetane and its excellent oil/water repellency.

Examples 14-20 show the preparation of additional R_(f) -substitutedoxetanes.

EXAMPLE 1 ##STR11##3,3-Bis(1,1,2,2-tetrahydroperfluorodecylthiomethyl)oxetane

3,3-Bis(bromomethyl)oxetane (15.0 g, 0.061 mol) is charged to a threeneck-flask with 1,1,2,2-tetrahydroperfluorodecyl mercaptan (62.3 g, 0.13mol). Toluene (90.0 g), distilled water (60.0 g) and sodium hydroxide(20.0 g, 50%) are added and the mixture is stirred under nitrogen.Tricaprylylmethylammonium chloride, a phase transfer catalyst, (0.5 g)is then added with stirring and the reaction mixture is heated to 95° C.under reflux for 2.5 hours. The toluene layer containing the product isseparated hot from the lower alkaline layer by a separatory funnel andcooled to precipitate the product. The product is filtered, washed threetimes with cold toluene and dried under vacuum to yield an off-whitesolid, mp 82° C.-83° C., 97% purity by GLC. NMR shows proton resonancesat 2.42 ppm, 4 protons, (2 ×CH₂ CH₂ S); 2.82 ppm, 4 protons, (2 33 CH₂CH₂ S); 3.09 ppm, 4 protons, (2 ×CH₂ CH₂ SCH₂); 4.56 ppm, 4 protons,(CH₂OCH₂).

Analysis for C₂₅ H₁₆ F₃₄ S₂ O;

Calculated: C, 28.8%, H, 1.5%, F, 62.0%, S, 6.2%.

Found: C, 28.6%., H, 1.3%, F, 61.7%., S, 6.6%.

EXAMPLE 2 ##STR12##3,3-Bis(1,1,2,2-tetrahydroperfluoro-octylthiomethyl)oxetane

3,3-Bis(bromomethyl)oxetane (15.0 g, 0.06 mol) is charged to athree-neck flask with 1,1,2,2-tetrahydroperfluoro-octyl mercaptan (51.08g, 0.134 mol). Toluene (90.0 9), distiled water (60.0 g) and sodiumhydroxide (20.0 g, 50%) are added, and the mixture is stirred undernitrogen. Tricaprylylmethylammonium chloride, a phase transfer catalyst0.5 g), is then added with stirring, and the reaction mixture is heatedto 95° C. under reflux for 1.5 hours. The toluene layer containing theproduct is separated from the lower alkaline layer and then cooled toprecipitate the product. The product is filtered cold, washed threetimes with cold toluene and dried under vacuum to yield an off-whitesolid, mp 45.5° C.-46° C., 99.5% purity by GLC. NMR shows protonresonances at 2.42 ppm, 4 protons, (2 ×CH₂ CH₂ S); 2.82 ppm, 4 protons,(2 ×CH₂ CH₂ S); 3.09 ppm, 4 protons, (2 ×CH₂ CH₂ SCH₂)., 4.45 ppm, 4protons, (CH₂ OCH₂).

Analysis for C₂₁ H₁₆ F₂₆ S₂ O;

Calculated: C, 30.0%, H,1.9%, F, 58.6%; S, 7.6%.

Found: C, 29.8%, H, 1.8%, F, 58.6%, S, 8.2%.

EXAMPLE 3 ##STR13##3,3-Bis(1,1,2,2-tetrahydroperfluorodecyloxymethyl)oxetane

1,1,2,2-Tetrahydroperfluoro-octanol (10.9 g, 0.03 mol),3,3-(bromomethyl)oxetane (3.9 g, 0.016 mol), potassium hydroxide (1.7 g,0.03 mol) and 15 9 of diethylene glycol dimethyl ether are reacted inthe presence of approximately 1.0 g of 18 Crown-6 in a 50 ml flask withgentle stirring for 72 hours at room temperature. Analysis by gaschromatography indicates that the solution contains 36% monoadduct and64% diadduct. 2.5 g of solids are filtered off and GC/MS identificationconfirms the presence of the desired3,3-(1,1,2,2-tetrahydroperfluoro-octyloxy)oxetane and3-(1,1,2,2,-tetra-hydroperfluoro-octyloxy)-3-bromo-oxetane.

Identification is made by GC/MS (E.I. Mode) after derivatization withN,O-bis-(trimethylsilyl)-trifluoroacetamide. Two major components areobserved:

(Diadduct)

MS: m/z 810 absent,780 (M-CH₂ O), 417 b.p., (M-C₆ F₁₃ CH₂ CH₂ O), 403(M-C₆ F₁₃ CH₂ CH₂ OCH₊₂). MS (CI) 811 (M+1)+

(Monoadduct)

MS: m/z 526 absent, 447 (M-Br), 417 b.p.(M-CH₂ OBr). MS (CI) 527 (M+1)+

EXAMPLE 4 ##STR14##3,3-Bis(1,1,2,2-tetrahydroperfluorododecyloxymethyl)oxetane

In a similar fashion to Example 3, 1,1,2,2-tetrahydroperfluorododecanolis reacted at 100° C. for 2-3 hours to give a mixture of monoadduct-40%and diadduct-60%.

EXAMPLE 5 ##STR15##3,3-Bis(N-ethylperfluoro-octanesulfonamidomethyl)oxetane

A mixture of N-ethylperfluoro-octanesulfonamide (20.0 9, 0.047 mol),potassium hydroxide (3.0 g, 0.047 mol), diethylene glycol dimethyl ether(60.0 g) and 18-Crown-6 ether (0.1g) is heated under nitrogen at 100°C.-105° C. for 30 minutes. The 3,3-bis-(bromomethyl)-oxetane (5.7 9,0.0236 mol) is then added, and the entire reaction mass is heated at100° C. for 13 hours. The salts are removed by filtration, and thesolvent is removed at 80° C. under vacuum. NMR shows the presence of theexpected product.

EXAMPLE 6 ##STR16##3,3-Bis(1,1,2,2-tetrahydroperfluorodecylsulfonylmethyl)oxetane

3,3-Bis(1,1,2,2-tetrahydroperfluorodecylthiomethyl)oxetane (15.0 g,0.014 mol) is dissolved in glacial acetic acid (44.27 g, 0.737 mol) andwarmed to 40° C. Hydrogen peroxide (4.0 g, 30%) is added, and themixture is stirred for 1 hour. The reaction mixture is then heated to100° C., and additional hydrogen peroxide (11.0 9, 30%) is added. Themixture is stirred for 2.5 hours under reflux. The product, a whiteprecipitate, is filtered, washed with ethanol and dried under vacuum,(13.85 g, 90% of theory) 93% purity by GLC. The product isrecrystallized from isapropyl acetate two times and dried under vacuumto yield a white solid (B.59 g, 56% of theory), mp 162° C.-4° C., 98%purity by GLC. NMR shows proton resonances at 2.90 ppm, complex, 4protons, (2 ×C₈ F₁₇ CH₂); 3.65 ppm triplet, 4 protons, (2 ×C₈ F₁₇ CH₂CH₂); 4.25 ppm, singlet, 4 protons, (2 ×CH₂ SO₂ CH₂); 4.80 ppm, singlet,4 protons, (oxetane ring).

Analysis for C₂₅ H₁₆ F₃₄ O₅ S₂ :

Calculated: C, 27.1%, H, 1.5%, F, 58.4%, S, 5.8%.

Found: C, 26.8%; H, 1.4%., F, 58.4%., S, 5.5%.

EXAMPLE 7 ##STR17##2,2-Bis(1,1,2,2-tetrahydroperfluorodecylthiomethyl)-3-iodo-1-propanol

3,3-Bis(1,1,2,2-tetrahydroperfluorodecylthiomethyl)oxetane (2.0 g, 0.010mol) is dissolved in tert-butyl alcohol (4.0 g, 0.054 mol). Hydriodicacid (1.0 g, 57%, 0.0045 mol) is added to the mixture, which is thenheated to 60° C. for 10 minutes. The product is precipitated from H₂ Oand then vacuum filtered. The product (1.65 g, 71% of theory) is ayellow solid, 92% purity by GLC. For analytical purposes, the crudeproduct is crystallized from heptane, which yields a white solid (1.30g, 56% of theory), mp 58° C.-60° C., 98% purity by GLC. NMR shows protonresonances at 2.43 ppm, complex, 4 protons, (2 ×C₈ F₁₇ CH₂); 2.72 ppm,singlet, 4 protons (2 ×SCH₂); 2.85 ppm, triplet, 4 protons, (2 ×CHX₂ S);3.55 ppm, singlet, 2 protons, (CH₂ I); 3.66 ppm, singlet, 2 protons,(CH₂ OH). OH is not observed.

Analysis for C₂₅ H₁₇ F₃₄ IOS₂ :

Calculated: C, 25.7%, H, 1.5%; F, 55.2%.

Found: C, 25.4%, H, 1.4%, F, 54.8%.

EXAMPLE 8 ##STR18##2,2-Bis(1,1,2,2-tetrahydroperfluorodecylthiomethyl)-3-chloro-1-propanol

3,3-Bis (1,1,2,2-tetrahydroperfluorodecylthiomethyl)oxetane (1.0 g,0.001 mol) is dissolved in tert-butyl alcohol (2.0 g, 0.054 mol).Hydrochloric acid (1.2 g, 37.7%, 0.011 mol) is added to the mixture,which is then heated to 60° C. for 10 minutes. The product isprecipitated from H₂ O (15 g), vacuum filtered and dried in a desiccatorover drierite. This procedure yields an off-white solid (0.40 g, 37% oftheory), mp 60° C.-1° C., 96% purity by GLC. NMR shows proton resonancesat 2.4 ppm, complex, 4 protons, (2 ×C₈ F₁₇ CH₂); 2.7 ppm, singlet, 4protons, (2 ×CH₂ S), 2.85 ppm, triplet, 4 protons, (2 ×SCH₂); 3.65 ppm,singlet, 4 protons, (CH₂ Cl and CH₂ OH). OH is not observed.

Analysis for C₂₅ H₁₇ ClF₃₄ OS₂ :

Calculated: C, 27.8%, H, 1.6%, F, 59.9%.

Found C, 27.6%., H, 1.3%., F, 59.5%.

EXAMPLE 9 ##STR19##2,2-Bis(1,1,2,2-tetrahydroperfluorodecylthiomethyl)-3-bromo-1-propanol

2,2-Bis(1,1,2,2-tetrahydroperfluorodecylthiomethyl)oxetane (7.0 g,0.0067 mol) is charged to a three-neck flask with hydrobromic acid (48%,2.5 9, 0.0015 mol) and toluene (20.0 g). The reaction is heated at 100°C. under nitrogen with stirring for 2 hours. The water/toluene azeotropeis then removed to 110° C. The toluene concentrate is then cooled andthe product precipitates. The product is filtered, washed three timeswith cold toluene and dried under vacuum to yield a white solid, mp 63°C.-64° C., 98% purity by GLC. NMR shows proton resonances at 1.70 ppm, 1proton, (--OH); 2.25-2.60 ppm, 4 protons, (2 ×R_(f) CH₂); 2.7-2.9 ppm, 8protons, (2 ×CH₂ --S--CH₂); 3.53 ppm, 2 protons, (CH₂ Br); 3.67 ppm, 2protons, (CH₂ OH).

Analysis for C₂₅ H₁₇ F₃₄ BrOS₂ :

Calculated: C, 26.7%; H, 1.5%, Br, 7.1%; F, 57.5%, S, 5.7%.

Found: C, 26.4%; H, 1.4%, Br, 7.3%; F, 55.9%, S, 6.1%.

EXAMPLE 10 ##STR20##2,2-Bis(1,1,2,2-tetrahydroperfluorooctylthiomethyl)-3-bromo-1-prapanol

3,3-Bis(1,1,2,2-tetrahydroperfluoro-octylthiomethyl)oxetane (7.0 g,0.0083 mol) is charged to a three-neck flask with hydrobromic acid (48%,3.1 9 0.018 mol) and toluene (20.0 g). The reaction is heated at 100° C.under nitrogen with stirring for 4 hours. The water/toluene azeotrope isthen removed at 110° C. The solvent is then removed under vacuum toyield a thick brown liquid which is 99% pure by GLC. NMR shows protonresonances at 1.80 ppm, 1 proton, (--OH), 2.2-2.6 ppm, 4 protons, (2×R_(f) CH₂); 2.7-2.9 ppm, 8 protons, (2 ×CH₂ SCH₂); 3.53 ppm, 2 protons,(CH₂ Br); 3.65 ppm, 2 protons, (CH₂ OH).

Analysis for C₂₁ H₁₇ OS₂ F₂₆ Br;

Calculated: C, 27.3%; H, 1.9%, Br, 8.7%, F, 53.5%, S, 7.0%

Found: C, 27.1%, H, 1.7%, Br, 9.1%, F, 51.5%, S, 7.1%

EXAMPLE 11 (C₈ F₁₇ CH₂ CH₂ SCH₂)₂ C(CH₂ Br)₂2,2-Bis(1,1,2,2-tetrahydroperfluorodecylthiomethyl)1,3-dibromopropane

2,2-Bis(1,1,2,2-tetrahydroperfluorodecylthiomethyl)-3-bromopropanol(10.0 g, 9 mmol) is charged to a three necked flask with phosphorustribromide (4.3 g, 16 mmol). The reaction mixture is heated at 100° C.under nitrogen for 2 hours to give the desired product which isrecrystallized from toluene.

Identification is made by GC/MS (EI mole).

MS: m/z 1184 (m+) 1165 (m-f), 739 (b.p.), 493.

EXAMPLE 12Poly-[2,2-Bis(1,1,2,2-tetrahydroperfluorodecylthiomethyl)-trimethyleneether]

3,3-Bis(1,1,2,2-tetrahydroperfluorodecylthiomethyl)oxetane (10.0 g,0.0096 mol) is dissolved in trifluorotrichloroethane and borontrifluoride etherate (2.0 ml) is added as catalyst. The reaction mixtureis stirred at room temperature for 0.5 hr. The product, a whiteprecipitate, is then vacuum filtered, washed two times withtrifluorotrichloroethane and dried under high vacuum, yielding a whitesolid (8.44 g). Several analyses confirm the presence of the desiredpolymer.

Analysis: for (C₂₅ H₁₆ F₃₄ S₂ O)_(n) :

Calculated: C, 28.8%, H, 1.5%., S, 6.1%.

Found: C. 26.6%., H, 1.5%, S, 6.0%.

The ¹ H NMR spectra obtained by silylation experiments indicates arepeat unit n, of 9-10.

DSC scans of the polymer were run at 10° C./min. to 350° C., 100 ml N₂/min. in open aluminum pans with a DuPont 990 Thermal Analyzer and a DSCcell base. The scans indicate an endothermic melting transition (T_(x)(extrapolated onset temperature) =116° C., T_(peak) =121° C.),irreversible decomposition transitions (T_(peak) =140° C. and 164° C.)and a major irreversible decomposition transition (T_(peak) =243° C.).

TGA scans were run at 10° C./min. to 550° C., 100 ml N₂ /min. using aDuPont 951 TGA module. The scans show a 22% weight loss from 150°C.-305° C. and a second weight loss of 73% from 305° C.-450° C. A 1%residue remains at 450° C. (A 4% weight loss before T=150° C. isattributed to solvent loss.)

Using the Zisman technique, the critical surface tension of the polymerγ_(c) is found to be 9.8 dyne/cm. This indicates that the polymer is oiland water repellent.

When a solution of said polyether in hexafluoroxylene is used to treat atextile surface to deposit 0.1% by weight thereon, the textile surfacesbecomes oil and water repellant.

EXAMPLES 13 TO 19

Using the methods described and by techniques similar to Examples 1-6,the following additional perfluoroalkyl substituted oxetanes areprepared.

    __________________________________________________________________________    Ex.                                                                              Thiol              Perfluoroalkyl Terminated Neopentyl                     __________________________________________________________________________                          Oxetane                                                 13 CF.sub.3 CF.sub.2 CH.sub.2 SH                                                                     ##STR21##                                              14 C.sub.6 F.sub.13 (CH.sub.2).sub.4 SH                                                              ##STR22##                                              15 C.sub.8 F.sub.17 CH.sub.2 CH.sub.2 CH.sub.2 SH                                                    ##STR23##                                              16 C.sub.8 F.sub.17 CH.sub.2 CH.sub.2 N(CH.sub.3)CH.sub.2 CH.sub.2               CH.sub.2 SH                                                                                       ##STR24##                                              17 C.sub.8 F.sub.17 SO.sub.2 NHCH.sub.2 CH.sub.2 OH                                                  ##STR25##                                              18 C.sub.8 F.sub.17 CH.sub.2 CH.sub.2 SO.sub.2 NHCH.sub.2 CH.sub.2                                   ##STR26##                                              19 C.sub.7 F.sub.15 CONHCH.sub.2 CH.sub.2 SH                                                         ##STR27##                                              __________________________________________________________________________

EXAMPLES 20 TO 27

Using the methods described and by techniques similar to Examples 7-12,the following additional alcohols, dihalides, esters and polymers areprepared.

    ______________________________________                                        Ex.   Product                                                                 ______________________________________                                        20                                                                                   ##STR28##                                                              21                                                                                   ##STR29##                                                              22                                                                                   ##STR30##                                                              23                                                                                   ##STR31##                                                              24                                                                                   ##STR32##                                                              25                                                                                   ##STR33##                                                              26                                                                                   ##STR34##                                                              27    Poly[2,2-bis(1,1,2,2-tetrahydrotrifluoropropyloxymethyl)-                     trimethylene ether]                                                     ______________________________________                                    

EXAMPLE 28 ##STR35##2,2-Bis-(1,1,2,2-tetrahydroperfluorodecylthiomethyl)-3-(2,3-dicarboxy-1-thiopropyl)-1-propanol

The bromohydrin of Example 9 (17.4 g, 16.6 mmol), diethyl thiosuccinate(6.5 9, 31 mmol), potassium carbonate (4.3 g, 31 mmol) and acetone (50ml) is charged to a three-neck flask and heated at reflux overnight.Water is added and the mixture extracted three times with methyl propylketone. The product is purified by silica chromatography to yield ayellow oil which is 99% pure by GLC.

The above diethyl ester (9.5 g, 7.6 mmol) is dissolved in 20 ml ofdiglyme and water (3 ml) in a single neck flask. Sodium hydroxide (1.5ml of a 50% aqueous solution) is added and the mixture allowed to stirovernight at room temperature. Water is added, and the mixture extractedwith methyl propyl ketone. The aqueous layer was acidified and extractedwith methyl propyl ketone. The solvent is removed under vacuum and theresultant yellow oil is precipitated into water to produce a whitesolid. NMR shows proton resonances at 2.5 ppm (4 ×R_(f) CH₂)., 2.6-3.0ppm (10 ×SCH₂ ; 3.51 ppm (2 ×CH2OH); 3.72 (1 ×SCHCO₂).

Analysis for C₂₉ H₂₂ F₃₄ S₃ O₅ :

Calculated: C, 29.2%, H, 1.8%, F, 54.1%, S, 8.1%.

Found: C, 28.9%, H, 1.7%, F, 53.9%, S. 8.2%.

EXAMPLE 292,2-Bis-(1,1,2,2-tetrahydroperfluorodecylthiomethyl)-1,3-(2-carboxy-1-thiaethyl)propane (C₈ F₁₇ CH₂ CH₂ SCH₂)₂ C(CH₂ SCH₂ CO₂ H)₂

The dibromide from Example 11 (25 g, 21 mmol), ethyl 2-mercaptoacetate(5.1 g, 41 mmol), potassium carbonate (5.8 g, 42 mmol), and acetone (70ml) is reacted and purified as described in Example 28.

The resultant diester is saponified, acidified and precipitated intowater to yield a white powder.

What is claimed is:
 1. A compound of formula I or II ##STR36## whereinR_(f) is a straight perfluoroalkyl of 1 to 18 carbon atoms, E isbranched or straight chain alkylene of 2 to 10 carbon atoms, or saidalkylene interrupted by one to three groups selected from the groupconsisting of --NR--, --O--, --S--, SO₂ --, --CONR--, --NRCO--, --SO₂NR--, and --NRSO₂ --, or terminated at the R_(f) end with --CONR-- or--SO₂ NR--, where R_(f) is attached to the carbon or sulfur atom, orR_(f) --E is CF₃ CH₂, and for formula I, X is --S--, --O--, --SO₂ --, or--NR--, or for formula II, X is --CONR--, --SO₂ NR--, or a direct bondwhere R_(f) is attached to the carbon or sulfur atom, and where R isindependently hydrogen, alkyl of 1 to 6 carbon atoms or hydroxyalkyl of2 to carbon atoms.
 2. A compound of formula I or II according to claim 1wherein R_(f) is a straight chain perfluoroalkyl of 1 to 12 carbonatoms.
 3. A compound according to claim 2 wherein R_(f) is a mixture ofC₄ F₉, C₆ F₁₃, C₈ F₁₇ and C₁₀ F₂₁.
 4. A compound of formula I accordingto claim 1 where R_(f) is perfluoroalkyl of 2 to 12 carbon atoms , E isalkylene of 2 to 6 carbon atoms, --CONHCH₂ CH₂ --, --CH₂ CH₂ N(CH₃)CH₂CH₂ --, --CH₂ CH₂ SO₂ NHCH₂ CH₂ --, --CH₂ CH₂ OCH₂ CH₂ --, or --SO₂NHCH₂ CH₂ --, and X is --S--, --SO₂ -- or --O--.
 5. A compound offormula I according to claim 1 wherein R_(f) is perfluoroalkyl of 6 to12 carbon atoms, E is ethylene, and X is --S--.
 6. A compound of formulaI according to claim 1 wherein R_(f) is perfluoroalkyl of 6 to 12 carbonatoms, E is ethylene, and X is --O--.
 7. A compound according to claim 1which is ##STR37##
 8. A compound according to claim 1 which is ##STR38##9. A compound according to claim 1 which is ##STR39##
 10. A compoundaccording to claim 1 which is ##STR40##
 11. A compound according toclaim 1 which is ##STR41##
 12. A compound according to claim 3 which is##STR42## where R_(f) is a mixture of C₄ F₉, C₆ F₁₃, C₈ F₁₇ and C₁₀ F₂₁.13. A compound according to claim 3 which is ##STR43## where R_(f) is amixture of C₄ F₉, C₆ F₁₃, C₈ F₁₇ and C₁₀ F₂₁.
 14. A compound accordingto claim 1 which is ##STR44## where R_(f) is a mixture of C₄ F₉, C₆ F₁₃,C₈ F₁₇ and C₁₀ F₂₁.